Trans-di(omega-alkenyl) cyclobutanes



United States Patent 5 Claims. (CL 260-666) This application is adivision of application Ser. No. 291,260, entitled,Trans-Dialiphatic-Substituted Cyclobutanes, filed June 28, 1963, nowU.S. Patent 3,356,705, issued Dec. 5, 1967.

The present invention is concerned with a novel process for theproduction of dialiphatic-substituted cyclobutanes, including polymericorganoaluminum compounds utilizing trans-divinylcyclobutane and anisoalkylaluminum as initial reactants. The invention is also concernedwith certain of the dialiphatic-substituted cyclobutanes, particularlythe polymeric organoaluminum compounds and the higher molecular weightdienes, monoand diepoxides, and diols hereinbelow described, as noveland useful composition of matter.

In accordance with this invention a trans-divinylcyclobutane, such astrans-1,2-divinylcyclobutane or trans-1,3- divinylcyclobutane, isinitially reacted with an isoalkylaluminum so as to form a novel polymercomprised of a major proportion of recurring trans-di(aluminoethyl)partial equation:

wherein each R, independently, designates an al-kyl radical preferablycontaining from 1 to 4 carbon atoms. The transdivinylcyclobutane canalso be substituted on the cyclobutane nucleus by alkyl or cycloalkylradicals.

It is to be noted that, as herein employed, the symbol a1 designatesone-third of an atom of aluminum. Thus, in all instances, each aluminumatom is attached to three other atoms. In addition, it is to be notedthat the dialuminoethylcyclobutane containing polymer is also comprisedof a minor amount of terminal aluminoalkane units derived, generally,from the isoalkylaluminum reactant. Minor amounts of other recurring andterminal units may also be present.

The isoalkylaluminums which can be reacted with transdivinylcyclobutaneas contemplated by this invention are the triisoalkylaluminums anddiisoalkylaluminum hydrides represented by the formulas:

II /R Al OHZCH and HA] onion ice proportion of trans-divinylcyclobutaneto isoalkylaluminum can vary broadly. Preferably, a proportion of fromabout 1 to about 5 moles of trans-divinylcyclobutane per mole ofisoalkylaluminum is char ed, although proportions outside this range canalso be employed. In addition, when desired, an inert organic solventcan be incorporated in the reaction mixture. Suitable solvents include,for instance, heptane, octane, decane, benzene, toluene, xylene, Decalinand the like.

The reaction temperature can vary broadly. Particularly good results canbe obtained, for instance, in the range of from about 70 C. to about 200C., substantially lower temperatures engendering an excessivly slow rateof reaction, while at higher temperatures, undesirable side reactionsmay occur. More preferably, a reaction temperature of from about C. toabout C. is employed. At such temperatures, the reaction is generallycarried out for a period of from about 1 to about 10 hours. However,longer or shorter reaction periods sufficient to produce the desiredpolymer can also be employed.

It has also been found preferable, during the course of the reaction, toremove the isoolefin formed as a by product. Concordant therewith, thereaction can be carried out in an open system under atmosphericpressure, or in a closed system under autogenous pressure, providing thesystem is equipped, in the latter instance, with means for venting orremoving the by-product. The removal of by-product isoolefin serves todrive the reaction to completion and minimizes or eliminates sidereactions between the isoolefin and the growing polymer.

The polymer thus obtained is ordinarily liquid at room temperature, andcan be recovered from the reaction mixture in any convenient manner. Forinstance, the polymer can be recovered as the residue product obtainedupon removal of the more volatile components of the reaction mixture bydistillation or evaporation, etc.

When a polymer containing recurring trans-di(aluminoalkyl) cyclobutaneunits of higher molecular Weight, i.e. increased aluminoalkyl chainlength, is desired, the polymer obtained as described above issubsequently subjected to a growth process by reaction with ethylene inthe absence of a catalyst, and preferably under pressure. This reaction,can be represented by the partial equation:

wherein y and z designate integers of from 0 to a positive value, atleast one of which must be a positive value as a consequence of thereaction with ethylene; the sum of y plus z being equal to x, the numberof moles of ethylene added per recurring unit of the polymer. Thus, inthe growth process ethylene units are inserted between aluminum atomsand adjacent carbon atoms. A similar growth process will also occur inany minor amounts of other recurring units present in the polymer, aswell as in terminal units. In addition, the grown polymer will contain aminor amount of recurring and terminal units which have not reacted withethylene.

The amount of ethylene reacted should be sufficient to effect the growthof the recurring units of the polymer to the extent desired, asdetermined, for instance, by the subsequent use of the grown polymer.Useful polymers, by way of illustration, are those in which thealuminoalkyl chain length of the recurring units have grown by astatistically varying length of from 2, and preferably from 6, to about32 carbon atoms, i.e. wherein y and z designate integers having a valuefrom zero to about 8, at least one of which has a positive value, thesum of which is preferably a value of at least 3. To this end, thepolymer for which growth is desired is reacted with ethylene in aproportion of at least 1.5 moles, and preferable from about 4.5 moles,to about 24 moles of ethylene per atom of aluminum present in thepolymer or per mole of isoalkylaluminum initially reacted to produce thepolymer. In practice, however, an excess over the required amount ofethylene is generally charged. If desired, an inert organic solvent suchas those described in connection with the initial polymer formation canalso be incorporated in the reaction mixture.

The reaction temperature for the growth process can vary broadly.Particularly good results can be obtained for instance, in the range offrom about 70 C. to about 200 C., substantially lower temperaturesengendering an excessively slow rate of reaction, while at highertemperatures, undesirable side reactions may occur, More preferably, areaction temperature of from about 80 C. to about 120 C. is employed,especially in connection with a batch operation. At such temperatures,the reaction is generally carried out for a period of from about 5 toabout 50 hours. However, longer or shorter reaction periods consistentwith the production of the grown polymer can also be employed. Thus, forinstance, the reaction can also be carried out continuously in a tubularreactor at a temperature preferably of from about 120 C. to about 190 C.for very short contact periods. The amount of ethylene entering thepolymer can be controlled in part by the control of temperature,reaction period, etc., and is readily determinable by one skilled in theart in light of this disclosure. Similarly, the reaction rate iscontrolled in part by the pressure, with pressures of from about 5,000p.s.i. being preferred.

After the desired amount of ethylene has been incorporated in thepolymer, as determined, for instance, by the moles of ethylene consumed,the system is vented so as to remove any excess ethylene. The grownpolymer thus obtained, like its polymeric precursor, is ordinarilyliquid at room temperature, and can be recovered from the reactionmixture in any convenient manner, as for instance, by the techniquesdescribed above in connection with the recovery of the ungrown polymer.

The grown polymer can be subjected to a displacement process bysubsequent reaction with ethylene, preferably in the presence of analuminum displacement catalyst and under pressure, to form a usefulclass of dienes, viz. trans-di(omega-alkenyl)cyclobutanes. This reactioncan be represented by the partial equation:

CHz=CH(GHzCHz)y +(CHaCHz) ZCH=CHZ ZaICHzCH;

wherein y and z are as defined above. When y or z is zero, it is to benoted, the adjacent vinyl group is attached directly to the cyclobutanenucleus. A similar displacement process also occurs in any minor amountsof other recurring units present in the polymer as well as in terminalunits.

In the displacement process, the polymer is reacted with ethylene in aproportion of at least 3 moles of ethylene per atom of aluminum presentin the polymer. In practice, however, an excess over the required amountof ethylene is generally charged. If desired, an inert organic solventsuch as those described above in connection with the initial polymerformation can also be incorporated in the reaction mixture. In addition,the presence of a small amount of an acetylenic compound, such asphenylacetylene, has been found to minimize the migration of doublebonds in the diene product.

Suitable aluminum displacement catalysts are known in the art andinclude nickel, cobalt, and platinum. Such metals can be incorporated inthe reaction mixture in ele- 4, mental form, or preferably, as aninorganic or organic salt, such as nickel chloride, platinum chloride,cobalt chloride, nickel acetylacetonate, platinum acetylacetonate,cobalt acetylacetonate, and the like. The use of such salts ordinarilyengenders a better dispersion of the metal in the reaction mixture. Thecatalyst is generally employed in a concentration of from about 0.001 toabout 1 percent by weight of metal based upon the weight of the polymerundergoing reaction, although higher or lower catalytic amounts can alsobe used. Preferably, the catalyst is employed in a concentration of fromabout 0.005 to about 0.1 percent by weight based in like manner.

The reaction temperature for the displacement process can also varybroadly, typically in the range of from about 25 C. to about 350 C.Particularly good results can be obtained in connection with a catalyticreaction in the range of from about 25 C. to about 200 C. Here again,substantially lower temperatures engender an excessively slow reactionrate, while at higher temperatures, in the presence of the catalyst,undesirable side reactions may occur. The more preferred catalyticreaction temperature is from about 40 C. to about C. At suchtemperatures, the reaction is generally carried out for a period of from1 to about 24 hours. However, longer or shorter reaction periodsconsistent with diene formation can also be employed. The displacementprocess can also be conducted omitting the use of a catalyst assubstantially higher reaction temperatures of up to about 350 C., orslightly higher, and preferably from 250 C. to about 320 C. At suchhigher temperatures, the reaction is best caried out continuously in atubular reactor for short contact periods.

The diene product thus obtained is ordinarily liquid at room temperatureand can be recovered from the reaction mixture by any of theconventional separation techniques described above. For instance, theproduct can be recovered as the residue obtained upon removal of themore volatile components of the reaction mixture by distillation.Alternatively, the reaction mixture can be hydrolyzed to assist theremoval of alkylaluminum formed as a by-product. Hydrolysis can beeffected by reaction with water, aqueous alcohol, and/or dilute acid.Upon hydro'lysis, aluminum hydroxide is formed. The diene product canthen be recovered by distillation of the organic phase of the reactionmixture. The removal of by-prod-uct alkylaluminum in this mannerprevents the reversal of the displacement process which might otherwiseoccur upon distillation of the diene product.

Due to the nature of the polymer employed as precursor, the dieneproduct may comprise an isomeric mixture oftrans'di-(omega-alkenyl)cyclobutanes of statistically varying molecularweight (alkenyl chain length). Such mixture can be resolved intocomponents of narrow carbon content ranges by fractional distillationand the products isolated and analyzed by gas chromatography.

As typical of the trans-di(omega-alkenyl)cyclobutanes produced inaccordance with this invention, there can be mentioned:

trans-1-(3-butenyl) -2-vinylcyclobutane,

trans-1 3 -butenyl 3 -vinylcyclobutane, trans-1,2 cli(-3-butenyl)cyclobutane, trans-1,3-di(3-butenyl)cyclobutane,

trans- 1% 5 -hexenyl -2-vinylcyclobutane,trans-1-(7-octenyl)-2-vinylcyclobutane,

trans-.1-( 3-butenyl -2-( 7 -octenyl) cyclobutane, trans- 1-( 5 hexenyl-2-'( 7-octenyl) cyclobutane, trans-L03 -butenyl) -2-'( S-hexenylcyclobutane, trans-1,2-di(5-hexenyl) -cyclobutane,-

trans- 1 ,'3-di( 5 -hexenyl cyclobutane, trans-\1-(9-decenyl)-2-vinylcyclobutane,

trans-l -(9-decenyl -3-vinylcyclobutane, trans-1,2-di(7-.octenyl)vinylcyclobutane,

trans- 1% 3-butenyl -2-( ll-d-odecenyl cyclobutane, transl 9-decenyl -2-(S-hexenyl cyclobutane,trans-l-(1l-dodecenyl)-L2-(i17-octadecenyl)cyclobutane,

CHzCH (CI'IgCHg) (CH3CH2) 5011 0112, and

/ CH CH (CHzC Hz) --(CHzCH2) 1C HCH:

' wherein y and z are as defined above.

The specific structure of the epoxide product will depend upon thetrans-di(omega-alkenyl)cyclobutane precursor; the formation of a mono-.or diepoxide being dependent, for the most part, upon the amount ofepoxidizing agent employed, and readily detenminable by one skilled inthe art in light of this disclosure. Mixtures of monoand diepoxides mayalso be produced depending, for instance, upon the amount of epoxidizingagent employed.

The epoxid-ation of the trans di(omega-alkenyl)cyclobutanes can becarried out by reaction with peracetic acid or other conventionalepoxidizing agent, in a suitable solvent such as ethylacetate, ifdesired, and at a temperature which can vary broadly in the range offrom about 25 C. to about 150 C. Preferably, reaction temperatures offrom about 10 C. to about 90 C. are employed. At such temperatures, areaction period of from about 1 to about 10 hours is usually sufiicientfor a complete reaction. However, longer or shorter reaction periodsconsistent with epoxide formation can also be employed.

The epoxide product can then be recovered from the reaction mixture inany convenient manner. For instance, the epoxide product can berecovered as the residue obtained upon removal of the more volatilecomponents of the reaction mixture by distillation or evaporation, andresolved, if desired, by further distillation when more than one epoxideis produced.

As typical of the trans vicinal monoand diepoxides produced inaccordance with this invention, there can be mentioned:

trans-tl-(B ,4-epoxy butyl) -2-( 1,2-epoxyethyl) cyclobutane, trans-1-(3,4-epoxybutyl) -2-vinylcyclobutane, trans-1-(3 butenyl)-2-( 1,2-epoxyethyl) cyclobutane, trans-1,2-di( 3 ,4-epo-xyb-utyl cyclobutane,{P211151 1-('3, 4-epoxybutyl) -'3-( 3-butenyl) cyclobutane, trans-l-(3,4-ep ox-ybutyl) -2-( 5,6-epoxyhexyl) cyclobutane, trans l(3,4-epoxybutyl) -2- S-hexenyl) cyclobutane, trans 1-( 3-butenyl) -'2 5,6-epoxyhexyl) cyclobutane, tran-s-1-( 9,|l O-epoxydecyl)-2-vinylcyclobutane, trans-1,2-di(7,8-epoxyoctyl) cyclobutane,trans-1-(7,8-epoxyoctyl)-3=(7-octenyl)cyclobutane,- trans-1-"( 11, 12-epoxydodecyl) -2 3,4-epoxybutyl) -cyc1obutane, transd filrl,IZ-epoxydodecyl) -2-*( 3-butenyl) cyclobutane, trans-14 1 1 -dodecenyl-2- ('3,4-ep oxybutyl) cyclobutane, trans-.14 3 ,4-epoxybutyl) -2-( 17,l 8-epoxyoctadecy1) cyclobutane, transl-( 3-butenyl -2- 17 l8-epoxyoctadecyl cyclobutane,

6 trans-1-(3,4-epoxybutyl) -2-( l7-octadecenyl cyclobutane, trans-l-( 11,12-epoxydodecyl)-2-(17,18-epoxyoctadecy1)cyclobutane, trans-l- (1l-dodecenyl -2-( l7, 1 S-epoxyoctadecyl cyclobutane, trans- 1- 11,12-epoxydodecyl -2-( l7-octadecenyl cyclobutane,

and the like. The higher molecular Weight epoxides of Formula Vcontaining from 10, and preferably 14, to about 40 carbon atoms arecontemplated as novel compositions of matter.

The trans vicinal monoand diepoxides produced in accordance with thisinvention can be homopolymerized or reacted with organic hardeners suchas polycarboxylic acids or anhydrides, polyamines, or polyols to producecurable resins having a wide variety of uses, particularly as moldedarticles. The resins thus obtained from the novel epoxides of thisinvention, particularly the diepoxides, may be characterized by enhancedimpact strength and thermal shock resistance. The novel dliepoxides ofthis invention can also be employed as plasticizers for vinyl resins.The novel monoepoxides of this invention, on the other hand, can becopolymerized with conventional vinyl monomers to produce resins havingenhanced heat and/ or light stability.

The polymers obtained in accordance with Equations I and III can also beconverted to a useful class of diols, viz, thetrans-di(omega-hydroxyalkyl)cyclobutanes represented by the formula:

wherein y and z independently designate integers of from 0 to 8. Thespecific structure of the diols will depend upon the polymer employed asa precursor. Thus, the diols represented by Formula VI wherein y and Zeach designate zero are derived from the polymer obtained in accordancewith Equation I; While the diols represented by Formula VI wherein 3and/or 1 designate a positive integer are derived from the grown polymerobtained in accordance with Equation III, with y and 2, being equal to yand z respectively.

The conversion of the polymer to diol can be carried out by contactingthe polymer at a temperature main tained in the range of from about 0 C.to about C., and preferably from about 30 C. to about 60 C., With oxygenso as to insert an oxygen atom between each aluminum atom of the polymerand the adjacent carbon atom. Such contact can be etfected, forinstance, by passing dry air or a nitrogen-oxygen mixture into areaction mixture containing the polymer. Since the reaction isexothermic, it is desirable in some instances to use a low concentrationof oxygen at the beginning of the reaction and thereafter increase theoxygen concentration in the reactant gas stream as the rate of reactiondecreases. Near the end of the reaction, pure oxygen can be used toinsure completion. If desired, an inert organic solvent such as thosedescribed above in connection with the initial polymer formation canalso be incorporated in the reaction mixture.

After the oxygenation step, water or dilute acid is added to thereaction mixture to convert the oxygenated polymer to the diol. Water ispreferred, as it readily hydrolyzes the polymer, forming the monoanddiols and aluminum hydroxide as a by-product. Alternatively, theoxygenated polymer can be hydrolyzed by reaction with aqueous alcohol.

The diol thus obtained can be recovered from the reaction mixture in anyconvenient manner, as for instance, by distillation of the organic phaseof the reaction mixture, etc. Moreover, due to the nature of thepolymers employed as precursors, the product may comprise an isomericmixture of trans-di(omega-hydroxyalkyl)cyclobutanes of statisticallyvarying molecular weight (hydroxyalkyl chain length). Such mixture canbe resolved into components of narrow carbon content ranges byfractional distillation and the products isolated and analyzed by gaschromatography.

As typical of the trans-di(omega-hydroxyalkyl)cyclobutanes produced inaccordance with this invention, there can be mentioned:

trans-1-(4-hydroxybutyl) -2-( 12-hydroxydodecyl cyclohutane,

trans-1-(10-hydroxydecyl)-2-(6-hydroxyhexyl)- cyclobutane,

trans-1-( -hydroxydecy1)-2-(8-hydroxyoctyl cyclobutane,

trans-1-( 12-hydroxydodecyl -2- 6-hydroxyhexyl cyclobutane,

trans-1-(4-hydroxybutyl-2-(14-hydroxytetradecyl)- cyclobutane,

trans-1-(4-hydroxybutyl) -2-( 18-hydroxyoctadecyl cyclobutane,

trans-1-(12-hydroxydodecyl)-2-(l8-hydroxyoctadecyl)- cyclobutane,

and the like. The higher molecular weight diols of Formula VI containingfrom 10, and preferably 14, to about 40 carbon atoms are contemplated asnovel compositions of matter.

The trans-di(omega-hydroxyalkyl)cyclobutanes produced in accordance withthis invention can be employed as organic hardeners by reaction withdiepoxides, such as 3,4-epoxy-6-methyl-cyclohexylmethyl3,4epoxy-6-methylcyclohexanecarboxylate, in conventional manner, toproduce curable resins having a wide variety of uses, particularly asmolded articles. The resins thus produced from the novel diols of thisinvention may be characterized by enhanced impact strength and thermalshock resistance.

The polymers obtained in accordance with Equations I and III can also behydrolyzed by reaction with water, aqueous alcohol and/or dilute acid toform the transdialkylcyclobutanes represented by the formula:

VII

the hydrolyzed product may comprise an isomeric mixture oftrans-dialkylcyclobutanes of statistically varying molecular weight(alkyl chain length). Such mixture can be resolved into components ofnarrow carbon content ranges by fractional distillation and the productsanalyzed by gas chromatography.

Trans-dialkylcyclobutanes can also be obtained by the reaction withhydrogen of the trans-di(omega-alkenyl) cyclobutanes of Formula IV inaccordance with conventional processes for the hydrogenation ofolefinically unsaturated compounds.

The invention can be illustrated further by the following examples. 7

Example I In a one-liter flask equipped with a stirrer, thermometer,condenser, inlet tube and attachment to a Dry Ice trap, 113 grams oftrans-1,2-divinylcyclobutane were added with stirring to 142 grams oftriisobutylaluminum, over a period of about two hours, at a temperaturemaintained in the range of from C. to 120 C. for a period of about 50minutes and at a temperature of from 115 C. to 140 C. for an additionalperiod of 10 minutes. During course of the ensuing reaction, 108 gramsof isobutylene, formed as a by-product, were removed. A polymericproduct comprised of recurring trans-1,2-di- (aluminoethyl)cyclobutaneunits was formed. The polymer was hydrolyzed first with aqueous ethanol,then With water. The hydrolysate was steam distilled to yield adistillate comprised of an upper organic layer and a lower aqueouslayer. The organic layer was separated, dried over magnesium sulfate,filtered, and distilled to yield 79 grams oftrans-1,2-diethylcyclobutane boiling at a temperature in the range offrom 110 C. to C. The aqueous layer and the residue from the steamdistillation were extracted with a petroleum ether (B.P. 35-37 C.) andcombined with the residue from the distillation of the organic layer.Distillation of this material yielded an additional 6 grams oftrans-1,2-diethylcyclobutane. The main cut (62 grams) oftrans-1,2-diethylcyclobutane had the following physical properties: B.P.114-115 C., 11 1.4096, 11 0.738. Literature: B.P. 115.5 C., 22 1.4128.Gas chromatography showed the presence of only one peak. In addition,the infrared spectrum and chromatography retention time were identicalwith the properties of trans-1,2-diethylcyclobutane produced by thehydrogenation of trans-1,2-divinylcyclobutane over platinum oxide. Inlike manner, a polymeric product comprised of recurringtrans-1,2-di(aluminoethyl)cyclobutane units is produced employingdiisobutylaluminum hydride as the isoalkylaluminum reactant.

Example II In a manner similar to that described above in Example I, 450grams of trans-1,2-divinylcyclobutane and 552 grams oftriisobutylaluminum were brought into reactive admixture to produce 571grams of a polymer comprised of recurringtrans-1,2-di(aluminoethyl)cyclobutane units. A mixture of 160 grams ofthis polymer, and 182 grams of ethylene was charged to a stainless steelbomb under a nitrogen atmosphere. The bomb was closed and heated,accompanied by rocking, at a temperature maintained in the range of from101 C. to 115 C. for a period of 3 hours, then at a temperaturemaintained in the range of from C. to 126 C. for a period of 18 hours,whereupon the pressure within the bomb dropped from a high of 920 p.s.i.at 103 C. to p.s.i. at 126 C. The bomb was vented at a temperature of 60C. The reaction product, a grown polymer comprised of recurringtrans-1,2-di(aluminoalkyl)cyclobutane units was hydrolyzed first withethanol, then with aqueous hydrochloric acid. A large volume of waterwas added to the hydrolysate, which formed an upper organic layer and alower aqueous layer. The organic layer was separated, washed with water,dried over magnesium sulfate, and distilled to yield the followingfractions:

The fractions were analyzed by gas chromatography and found to becomprised in major amount of trans-1,2- 1 2 6 8 10) 12 14 2 16 18" 20 z2and ar' alkyl)cyclobutanes, i.e. cyclobutanes containing two alkylsubstituents in trans-1,2 position, the substituents possessing anaggregate sum of 4,6,8,10,12,14,16,18,20,22, and 24 carbon atoms.

Example III An ethylenically grown polymer obtained as described abovein Example II is dissolved in benzene at a temperature of about 60 0.,dry air is passed through the solution thereby oxygenating the polymer.Upon completion of the ensuing reaction, as evidenced by a cessation inthe evolution of heat, water is added to the reaction mixture,accompanied by heating at a temperature of about 100 C., to hydrolyzethe polymer. The precipitated aluminum hydroxide is removed byfiltration. The filtrate is thereafter fractionally distilled. In thismanner 1 s C6: C8": 12-, 14-, C16: C 0 C and C-di[omega-hydroxyalkyl])cyclobutanes, i.e. cyclobutanes containing twoomega-hydroxyalkyl substituents in the trans-1,2 position, thesubstituents possessing an aggregate sum of 4, 6, 8, 10, 12, 14, 16, 18,20, 22, and 24 carbon atoms, are obtained as products. Upon similarreaction of the polymer obtained as described above in Example I,trans-l,2-di(2-hydroxyethyl) cyclobutane is obtained as a product.

Example IV In a manner similar to that described above in Example I,trans-1,2-divinylcyclobutane was reacted with triisobutylaluminum toproduce a polymer comprised of recurringtrans-1,2-di(aluminoethyl)cyclobutane units. A mixture of 260 grams ofthis polymer, and 300 grams of ethylene was charged to a stainless steelbomb under a nitrogen atmosphere. The bomb was closed and heated,accompanied by rocking, at a temperature maintained in the range of from108 C. to 114 C. for a period of 38 hours, whereupon the pressure in thebomb dropped from a high of 1,520 p.s.i. to 425 p.s.i. An ethylenicallygrown polymer comprised of recurring trans-1,2di(aluminoalkyl)cyclobutane units was formed. The bomb was cooled andvented at a temperature of 70 C. To the contents of the bomb, 290 gramsof additional ethylene, 345 grams of benzene, and 0.1 gram of nickelacetylacetonate were added at room temperature. The bomb was closed andreheated, accompanied by rocking, at a temperature maintained in therange of from 68 C. to 73 C. for a period of 19 hours, whereupon thepressure in the bomb dropped from a high of 825 p.s.i. to 450 p.s.i. Thebomb was vented at a temperature of 40 C. and the reaction product washydrolyzed, together with a benzene rinse, first with aqueous ethanol,then with water. A two-phase mixture comprising an upper organic layerand a lower aqueous layer was formed. The organic layer was separated,dried over calcium chloride, and distilled to yield the followingfractions after the removal of lower boiling material:

Weight Fraction Grams B.P. O.) 0,. range 1 76 80/atm.-90/200 mm. Hg Ca2.. 51 62/50 111111. Hg.70/5 mm. Hg Ca -C12 3. 69 70/5 mm. Hg./1 mm. HgC r-C 4. 40 /1 mm. Hg.200/1 mm. H 5- 10 2110/1 mm. Hg.210/l mm. Hg 6 21210/1 mm. Hg.-240/0.3 mm. Hg Residue. 49

Fractions 1 to 3 were analyzed by gas chromatography and found to becomprised in major amount of trans-1,2- (C C5", 0 C and C-di[omega-alkenyl] )cyclobutanes, i.e., cyclobutanes containing twoomega-alkenyl substituents in trans-1,2 position, the substituentspossessing an aggregate sum of 4, 6, 8, 10 and 12 carbon atoms.Fractions 4 to 6 are comprised of higher molecular weighttrans-1,2-di(omega-alkenyl)cyclobutanes containing an even number ofcarbon atoms,'such as trans-l,2-(C

butanes.

A trans-1,2-(C -di[omega-alkenyl])cyclobutane thus obtained, such :astrans-l,2-di(5-hexenyl)cyclobutane, is converted to the correspondingdiepoxide, viz. trans-1,2- di(5,6-epoxyhexyl)cyclobutane, by admixingthe diene, inethyl acetate, with an excess over two moles of peraceticacid per mole of diene and heating the resulting mixture at atemperature of about 60 C. for a period of several hours. Upon usingless than two moles of peracetic acid per mole of diene in an otherwisesimilar process, a mixture oftrans-l-(S-hexenyl)-2-(5,=6-epoxyhexyl)cyclobutane andtrans-1,2-di(5,6-epoxyhexy)cyclobutane is produced and subsequentlyresolved by distillation. In like manner, othertrans-1,2-diQomega-alkenyl)cyclobutanes produced as described above inthis example are converted to the corresponding monoand diepoxides byreaction with peracetic acid.

What is claimed is:

1. The process for the production of a trans-di(omegaalkenyl)cyclobutaneof the formula:

wherein y and z designate integers of from 0 to 8, at least one of whichis a positive integer, which process comprises the steps of (a) bringingtrans-divinylcyclobutane into reactive admixture with anisoalkylaluminum of the formula selected from the group:

R R Al C HaC iI and HA1 CHQCE R a R 2 wherein each R, independently,designates an alkyl radical of from 1 to 4 carbon atoms, at atemperature of from about 70 C. to about 200 C., and while removing theisoolefin formed as a by-product from the resulting mixture, for aperiod of time suflicient to produce a polymer comprised of recurringunits of the formula:

[alC H O H+ +0 HBC Hgal] '(b) bringing said polymer into reactiveadmixture with at least 1.5 moles of ethylene per aluminum atom of saidpolymer, in the absence of a catalyst, at a temperature of from about 70C. to about 200 C., for a period of time suflicient to produce anethylenically grown polymer comprised of recurring units of the formula:

wherein y and z are as defined above; and (c) bringing saidethylenically grown polymer into reactive admixture with at least 3moles of ethylene per aluminum atom of said ethylenically grown polymer,at a temperature of from about 25 C. to about 350 C., and in contactwith a catalytic amount of an aluminum displacement catalyst when saidtemperature is in the range of from about 25 C. to about 200 C., for aperiod of time sufficient to produce said di(omega-alkenyl)cyclobutane.

2. The process for the production of a trans-di(omegaalkenyl)cyclobutane of the formula:

wherein y and z designate integers of from to 8, at least one of whichis a positive integer, which process comprises the steps of (a) bringingtrans-divinylcyclohutane into reactive admixture with anisoalkylaluminum of the formula:

/R /R A1 CH CH and HA1 CHzCH R a R 2 wherein each R, independently,designates an alkyl radical of from 1 to 4 carbon atoms, at atemperature of from about 90 C. to about 160 C., and while removing theisoolefin formed as a by-product from the resulting mixture, for aperiod of time sufiicient to produce a polymer comprised of recurringunits of the formula:

[alC HgCH+ +0 H O Hzal] wherein y and z are as defined above; and (c)bringing said ethylenically grown polymer into reactive admixture withat least 3 moles of ethylene per aluminum atom of said ethylenicallygrown polymer, in contact with a catalytic amount ofnickelacetylacetonate, at a temperature of from about 40 C. to about C., for aperiod of time sufficient to produce said di(omega-a1keny1)cyclobutane.

3. The process according to claim 2 wherein said isoalkylaluminum istriisobutylaluminum.

4. The process according to claim 2 wherein said transdivinylcyclobutaneis trans-1,2-divinylcyclobutane.

5. The trans-di(omega-alkenyl)cyclobutane of the for mula:

wherein y and z are integers of from 0 to 8, the sum of which is a valueof at least 3.

References Cited UNITED STATES PATENTS 3,035,077 5/1962 Johnson et a1.260-448 3,136,667 6/1964 DAlelio 149- 19 3,294,863 12/1966 De Acetis eta1 260-830 3,325,524 6/1967 Lundeen 260448 2,960,541 11/1960 Elam et al.260648 3,308,143 3/1967 Poe et a1 260683.15 3,309,416 3/1967 Poe et a1.260683.15 3,347,894 10/1967 Trebillon et a1. 260-448 3,356,705 12/1967Marcus 260-448 OTHER REFERENCES George S. Hammond et al.: J. Org. Chem.,28, pp. 3297-3303, 1963.

DELBERT E. GANTZ, Primary Examiner. V. OKEEFE, Assistant Examiner.

1. THE PROCESS FOR THE PRODUCTION OF A TRANS-DI(OMEGAALKENYL)CYCLOBUTANEOF THE FORMULA: